Nongorrosive detergent



Patented May 1, 1951 UNITED STATES IEATENT OFFICE NONCO'RROSIVEDETERGENT COMPOSITIONS Jay C. Harris, Daytonpohio; assignor to Mon,

santo Chemi'calCompany, St. Louis, Mo., acorporation 01 Delaware No,Drawing. Application November 25; 1949, Serial No. 129,539

disclosed the condensation product of tall oil with ethylene oxide,said, condensation products containing at least 0.5 part, but. lessthan. 2.3 parts; of ethylene:oxideper'partzoftali oil. There is alsodisclosed in the same application a combination of the said condensationproducts with; 20

alkaline builders, such as the sodiumphosphates, particularlytetrasodium pyrophosphate; soda? ash, starch, etc. The compositions soproduced are highly efiicient detergents.

I have now found that when such compositions as above disclosed areemployed in automatic laundry machinery, such. as household washingmachines, constructed in whole or in part of aluminum or. of vitreousenameled steel,,

the. surfaces of these devices in contact with 30 detergent solutionsare etched or corroded so as to lead to an undesirable roug hening ofthe surfaces, so exposed, and in some cases to failure of' the vitreouscoating.

I have also discovered that substantially com- 35" plete protection ofsuch surfaces can be obtained by including in the detergent compositionsfrom 6% to 25% by weight, based upon the combined weight of phosphatesand carbonates of a-solublesodium silicate, wherein the Na2O:SiOz-molera- 4'0 ho is between, 1:2 to 113.2. The percentage of the silicatestated above is based upon the anhydrous form. Any water soluble formofsodium silicate maybe employed. The phosphates and carbonates in thecomposition maybe in the hy- 4'5 drated or anhydrous form; however; whenin the hydrated form allowance shouldbe made for the. amountof waterpresent order'to maintain the ingredients when dissolved in. waterwithin the 'efiective :rangeror proportions disclosed and; .50.

7; Claims; (:01. 252440);

claimed. The percentage of sodium silicate is therefore based upon theanhydrous phosphates and carbonates present in the composition. Solublesilicates may be in solid form or they may V be employed in aqueoussolutions, which solutions may contain up to-85%- of'water.

The present composition also contains tetrasodium pyrophosphate or thesodium tripolyph'os phate, NaaPaOm, either in anhydrous or hydratedform; Perfumes such as- Citropene may be added if desired. i

The constitution of the sodium silicates employed should be maintainedwithin the limits stated so that the silicates will dissolve in thedetergent solution at a rate sufficiently rapid so that they will beeiiective forcorrosion prevention: from the instant of solution: ofthedetergent. They should, moreover, be employed in the amount statedabove, since I' have found that quantities below the lower limit givenare inei--- fective for the. purpose, while quantities above the upperlimit. are undesirable, because of an adverse effect upon the detergentefficiencyoithe composition.

The preferred propcrtions of the ingredients in the present product,together with: the range of ingredients efiective for the presentpurpose, areas iollows, all parts being by weight:

Condensation product of tall oil with ethylene'oxide in the ratioof0.5":2L3 per part of tall oil '10 -25- Tetrasodium pyrophosphate, sodiumtripolyphosphate, or mixtures thereof (an-- hydrous basis) 20-60' Sodiumsilicate, Na2O:SiOz ratio of 1:2' to 1:312 (anhydrous basis) StarchAlkaline material selected fromthe class consisting of sodium carbonate,sodium bicarbonate and mixtures thereof (anhydrous'basis) 10-25 To theabove product may bev added from 0.1-

to 5 parts of carboxy methyl cellulose:

For washing soiled textiles, the above composi-- tions are dissolved. inhot water. to give; prefer ably a 0.1% to 0.25%: by weight solution, although other concentrations may also be em- Parts 3 The following morespecific examples illustrate the invention:

EXAMPLE 1 A composition consisting of an intimate mixture of thefollowing ingredients is prepared, the proportions being based on theanhydrous salts.

Parts Condensation product of one part of tall oil with 1.6 parts ofethylene oxide 15.00

. Tetrasodium pyrophosphate 40.00

Soda ash 20.25 Solid sodium silicate (G Silicate) Na2O:SiO2=1:2 24.00

Carboxy methyl cellulose 0.75

Total 100.00

EXAMPLE 2 Parts Condensation product of one part of tall oil with 1.8parts of ethylene oxide 20 Sodium tripolyphosphate 40 Sodium carbonate15 Sodium silicate (anhydrous) I NaaO:SiOz=1:3.2 1 Starch 14 Carboxymethyl cellulose 1 Total 100 EXAMPLE 3 Parts Condensation product of onepart of tall I oil with 1.6 parts of ethylene oxide 15.00 Tetrasodiumpyrophosphate (anhydrous basis) 40.00

Soda ash 20.15 Sodium silicate solution (water glass, 38%

solids, 62% water) Na2O:SiO2=1:3.2 24.00 Carboxy methyl cellulose 0.75Perfume (Citropene) 0.10

' Total 100.00

The above compositions provide excellent detergency without noticeableaction on vitreous enamel or aluminum washer baskets.

The composition presented in Example 3 above may be formed by mixing thecondensation product with the finely ground tetrasodium pyrophosphateand soda ash, then adding the liquid sodium silicate, followed by theremaining ingredients. The water contained in the silicate solution.will hydrate the anhydrous salts forming hydrated salts. The quantityof water glass employed (24 parts), since it contains about 62% ofwater, will furnish sufficient water to hydrate the soda ash to thesodium carbonate monohydrate, and somewhat less than half of thetetrasodium pyrophosphate to the decahydrate. This composition,therefore, contains 15 by Weight of water of hydration. Additional watermay be added if desired in order to more completely hydrate thesalts. Byso hydrating the salts either partly or completely in the presence ofthe condensation product a better retention of the oily condensationproduct is obtained. is more fully described and claimed in copendingapplication to Louis E. Wells and Henry V. Moss, Serial No. 92,954,filed May 12, 1949, which application is assigned to the same assigneeas is the present case.

When water is added to the composition either in the form of an aqueoussilicate solution or as such, it may be added in amount sufficient tohydrate the tetrasodium pyrophosphate at least to an average of 3.5moles of water, but not in excess of 10 moles of water per mole oftetrasodium pyrophosphate. A range of from 35 moles to 5 moles of wateris preferred in practice. When sodium tripolyphosphate is employed inthe composition, from 3 to 6 moles of water may be employed, the lowerlimit (3 moles) per mole of sodium tripolyphosphate being preferred.Soda ash is advantageously hydrated to the monohydrate, whereas sodiumsesquicarbonate is hydrated to 2 moles of water per mole ofsesquicarbonate.

The order of addition It has been found that when an amount of waterequivalent to 10 moles of water per mole of tetrasodium pyrophosphate isemployed the initially formed product is quite damp. However, upon agingfor several days at room temperature a satisfactory dry product isobtained.

The amount of sodium silicate employed should be from 6 to 25 parts per20 to 60 parts of phosphate and 10 to 25 parts of the carbonate reckonedon theanhydrous basis. By employing these proportions excellentdetergency is obtained without encountering corrosion of vitreousenameled or aluminum surfaces. Within these limits the product does notabsorb excessive amounts of moisture from'humid air under conditionsordinarily encountered in the use of the detergent. The detergentremains free-flowing, exhibiting no tendency to cake due to the silicatepresent.

Corrosion tests made by exposing weighed pieces of aluminum metal of thesame area (49.9 sq. cm.) to,0.25% aqueous solutions of various detergentcompositions at a temperature of F'., gave the following weight lossesin duplicate tests. Each exposure was for 10 minutes and a total of 10exposures were made before final weighing.

GramsLoss in Product Tested Welght 1 0.0107 and 0.0112 2 0.0041 and0.0047 3 0.0071 and 0.0006 0.0018 and 0.0015

Tall oil-ethylene oxide condensation product 'Ietrasodium pyrophosphate40. 0

The hydration reaction taking place when aqueous sodium silicates areemployed may evolve a considerable amount of heat, particularly when thefreshly prepared composition is allowed tostand in large piles. product.

This results in a lump shallow piles or layers which are on the order ofone foot in thickness. Alternatively the mixed material may be placedupon a moving belt in a layer several inches thick, which layer is thencaused to be discharged upon another moving belt until such time as thehydration reaction has been completed and then into suitable storagereceptacles. When this has occurred the material is a non-caking andfree-flowing powder.

What I claim is:

1. A detergent composition comprising the following essentialingredients in parts by weight:

said composition containing in addition from 6% to 25% by weight, basedon the combined weight of said phosphate material and said alkalinematerial, of a, sodium silicate having an NazO2SiOz ratio of from 1 :2to 1 :32.

2. A detergent composition comprising the following essentialingredients:

Parts Condensation product of tall oil with ethylene oxide containingfrom 0.5 part to 2.3 parts of ethylene oxide per part of tall oil Asodium phosphate selected from the group consisting of Na4P2O7 andNasPaOw (anhydrous basis Sodium silicate NazOzSiOz ratio from 1:2 to1:32 (anhydrous basis) Alkaline material selected from the groupconsisting of sodium carbonate, sodium bicarbonate and mixtures thereof(anhydrous basis) 10-25 3. A detergent composition comprising thefollowing essential ingredients:

Parts Condensation product of one part of tall oil with 1.6 parts ofethylene oxide 20.00 Tetrasodium pyrophosphate 40.00 Soda ash 20.15

Solid sodium silicate, Na2O:SiOz=1:2 15.00 Carboxy methyl cellulose 0.75

5. A detergent composition comprising the following essentialingredients:

Parts Condensation product of one part of tall oil with 1.4 parts ofethylene oxide 20 Tetrasodium pyrophosphate (anhydrous basis) 40 Sodiumsesquicarbonate (hydrated basis) 18 Sodium silicate (anhydrous)Na2O:SiO2=1:2 20 Carboxy methyl cellulose 2 6. The process whichcomprises dissolving in water a detergent product having a compositionas defined by claim 1 to form a detergent solution and then washingtextiles therewith, said washing process being conducted in the presenceof vitreous enameled or aluminum surfaces, whereby corrosion of saidsurfaces normally occurring in the absence of the sodium silicatecontained in said product is substantially prevented.

7. The process which comprises dissolving in water a detergent producthaving a composition as defined by claim 2 to form a detergent solutionand then washing textile products therewith, said washing process beingconducted in the presence of vitreous enameled or aluminum surfaces,whereby corrosion of said surfaces normally occurring in the absence ofthe sodium silicate contained in said product is substantiallyprevented.

JAY C. HARRIS.

REFERENCES CITED The following references are of record in the file ofthis patent:

UNITED STATES PATENTS Name Date Nuesslein Nov. 23, 1943 FOREIGN PATENTSCountry Date Great Britain July 23, 1937 Great Britain Jan. 9, 1939OTHER REFERENCES Number Number

1. A DETERGENT COMPOSITION COMPRISING THE FOLLOWING ESSENTIALINGREDIENTS IN PARTS BY WEIGHT; CONDENSATION PRODUCT OF TALL OIL WITHETHYLPARTS OF ETHYLENE OXIDE PER PART OF TALL ENE OXIDE CONTAINING FROM0.5 PART TO 2.3 A PHOSPHATE MATERIAL SELECTED FROM THE GROUP CONSISTINGOF TETRASODIUM PYROPHOSPHATE AND SODIUM TRIPOLYPHOSPHATE ALKALINEMATERIAL SELECTED FROM THE GROUP CONSISTING OF SODIUM CARBONATE, SODIUMBICARBONATE AND MIXTURES THEREOF (ANSAID COMPOSITTION CONTAINING INADDITION FROM 6% TO 25% BY WEIGHT, BASED ON THE COMBINED WEIGHT OF SAIDPHOSPHATE MATERIAL AND SAID ALKALINE MATERIAL, OF A SODIUM SILICATEHAVING AN